US 3064044 A
Description (OCR text may contain errors)
Nov. 13, 1962 R. H. BALDWIN MULTISTAGE OXIDATION SYSTEM FOR PREPARING DIcARBOxYLIc ACID Filed Aug. 15. 195'? llnited States Patent Bhddldi Patented Nov. 13, 1962 3,064,044 MUJTESTAGE @XlDATiON SYSTEM FR PREPRHQG DECRBXYLIC ACH) Richard H. Baldwin, Chicago, Ill., assigner to Standard @il Company, Chicago, Ill., a corporation of Indiana Filed Aug, 1S, i957, Ser. No. 678,298 4 lainis. Si. 26h-624) This invention relates to a multistage oxidation system for oxidizing an aromatic hydrocarbon having at least one, and preferably two or more, oxidizable substituents into a carboxylic acid product and it pertains more particularly to an improved technique for maintaining a iinal oxidation under substantially anhydrous conditions. The invention will be described as applied to the production of terephthalic acid from paraxylene.
An object of th invention is to provide improvements in commercial systems for obtaining maximum yields of high quality aromatic carboxylic acids by the oxidation of aromatic hydrocarbons having oxidizable substituents in the presence of known oxidizing catalysts wherein a bromine-attording substance is employed in at least the final oxidation stage which is operated at a pressure in the range of 5G to 5G() p.s.i. at a temperature in the range of about 32) to 440 F. A further object is to provide an improved technique for handling solvent (preferably acetic acid) and for maintaining the solvent in the iinal oxidation zone under substantially anhydrous conditions. @ther objects will be apparent as the detailed description ofthe invention proceeds.
in practicing the invention an aromatic hydrocarbon having at least one, and preferably two or more, oxidizable substituents such, for example, as substantially pure paraxylene is continuously oxidized with an oxygen-con taining gas such as air in a stage-countercurrent oxidation system wherein the first stage is operated at about 50 to 40G psi. at a temperature in the range of 30) to 400 F. for a period of .1 to 2 hours or more and the second stage is operated under a pressure of about 100 to 560 p.s.i. at a temperature in the range of about 320 to 440 F. for an average contacting period of about .2 to 2 hours, a solvent or reaction medium being employed in both stages. The
solvent is preferably an aliphatic carboxylic acid having 2 to 6 Carbon atoms per molecule and the preferred solvent is acetic acid. The amount of solvent should be at least about 1:1 on a volume kbasis in each stage based on charging stock and may be as high as 5:1 or more, the amount in any case being sufficient to give a readily transferable and pumpable slurry. Temperature control in each of the oxidation zones is preferably ehfected by removing vapors of aqueous solvent at a predetermined controlled pressure. By introducing large amounts of substantially anhydrous solvent into the final oxidizing zone, the water produced in said zone is largely removed in vapor form with solvent vapors so that the solvent ccnccntration in this final stage can be maintained higher than 90 percent and preferably hivher than 95 percent by weight. The aqueous solvent vapors removed from eachY of the zones is at least partially condensed and at least a part of the resulting condensate is introduced to the first stage oxidation zone in order to supply the required amount of solvent therein. Thus while some anhydrous solvent may be introduced to the first stage and some aqueous solvent condensate may be returned to the second stage, most of the second stage solvent is introduced thereto in substantially anhydrous form while in the rst stage more solvent is introduced in condensed aqueous form than is introduced in anhydrous form.
lf desired, the product trom the first stage may be flashed to remove therefrom any unoxidized hydrocarbons and these unoxidized hydrocarbons may be returned to the rst stage sothat Ipartially oxidized hydrocarbons are finally `oxidized in the second stage.
The invention will `be more clearly understood from the following detailed description of a specific example read in conjunction with the accompanying drawingwvhich is a schematic owsheet of a continuous oxidation and acid recovery system embodying the present invention.
The substituted aromatic which is to undergooxidation, paraxylene in this example, is introduced through line 10 at a controlled temperature into reactor 11 along with aqueous solvent condensate from line 12, the solvent in this case being acetic acid. About l to 2 weight percent of manganese bromide based on fresh paraxylene is introduced via line i3, preferably with aqueous solvent introduced by line 12. although, if desired, the manganese may be added to the first stage in the form of manganese acetate and. another -bromine-affording substance such as ammonium bromide may be introduced directly into the secondstage.
No novelty is claimedy per se in the catalyst or in the catalyst promoter employed in this invention since the invention is an improvement in a particular promoted catalyst system recently perfected by others. The catalyst is a multi-valent or heavy metal, preferably iny a form which isr soluble in the reaction medium or solvent. The catalyst metal may advantageously be selected from the group consisting of manganese, cobalt, nicxel, chromium, vanadium, molybdenum, tungsten, tin, cerium, or mixtures thereof, and theA metal may -be employed in elemental, combined, or ionic form-preferably in the form of acetate when the reaction medium or solvent is acetic acid. The promoter is a substance-affording bromine, they bromine being in elemental, ionic, organic or inorganic form. Thus the bromine may be employedy in the form of potassium bromate, ammonium bromide, benzylbromide, tetrabromoethane, manganese bromide or; the like. The proportions of catalyst. and promoter maybe approximately stoichiometric as exemplified. by manganese bromide and generally are'in the range of 1:.10 to 16:1 atoms of catalyst metal per atom or bromine. The amount of catalyst employed is usually in the range of about .0l to l0 percent or more and is preferably inthe range of about .2 to 2' percent by weight based on aromatic hydrocarbon reactant charged. The preferred mixed metal catalysts are mixtures of manganese in the form of bromide or acetate with ammonium molybdate,
ammonium chromate, tungstic acid, cobalt acetate, or the like, the proportions usually being about 1 to 2 parts' by weight of the manganese salt per part by weightof ther other metal compound. Alternatively, of course7 the catalyst metals may be employed as salts of anV acid which is being produced in the system.
The oxidizing gas introduced atthe base of. vessel 1l may be oxygen-containing gas from line M'supplemented with a controlled amount of air introduced via line. l5 to the base of vessel il. This vessel is preferably providedwith one or more baffles ld for separating the vessel'intoV separate stages and each stage of the' vessel is provided with impeller mixers 17 and i8 which are rotated at such speed as to obtain intimate mixing and to prevent.' product solids or catalyst from settling out of the liquid phase.` Vessel l1 is operated in this example at about 225 p.s.i. and at a temperature of about. 375 F. with an average holding time of about l hour, vapors are removed through line i9 and cooled in condenser 20, theV resulting, condensate and uncondensed gas being introduced into reeeiver 2l.. Condensate which is largely aqueous solvent is withdrawn from the receiver -by line 22 and'that portion.
thereof which is not returned by line 23 to vessel ll. is introduced by line 24 to still 25. Uncondensed gas which leaves the top of receiver 2l through line 26 is scrubbed in vessel 27 with Water from line 28 so that the gases ultimately vented through line 29 contain no acetic acid. Aqueous acetic acid from the base of scrubber 27 is returned by line 30 and line 24 to still 25.
The partially oxidized charge is withdrawn from vessel 11 by line 31 and it may be pumped directly by pump 32 to the second stage oxidizing vessel 33. However, it may be desirable to introduce into vessel 33 only partially oxidized hydrocarbon such as toluic acid, in which case the liquid from the base of vessel 11 may be introduced through pressure reducing Valve 34 into ash chamber 35 from which vaporized hydrocarbons are returned through condenser 36 by pump 35 to vessel 11 and only the partially oxidized products are transferred by line 38 and pump 32 to second stage oxidizer 33. In either case, suicient air is introduced at a controlled rate by line 39 at the base of vessel 33 to complete the oxidation of the paraxylene to terphthalic acid. In addition to partially oxidized material from vessel 11, recycled partially oxidized material, such as toluic acid, may be introduced to oxidizer 33 by line 40. If manganese acetate is employed as the sole catalys-t in vessel 11, a bromine-affording material such as ammonium bromide is introduced through line 41 in an amount of the order of .1 to 1 weight percent based on charge.
Oxidizer 33 is maintained at a pressure of about 400 psi., at a temperature of about 400 F., the temperature being controlled by adding substantially anhydrous acetic acid to the various stages through lines 42 and 43V and removing aqueous solvent vapors through line 44 and condenser 45 to receiver 46. The uncondensed gas leaving the top of receiver 46 should contain less than 8 percent oxygen but it may contain about l to 8 percent oxygen and hence it is introduced by lines 14 and 15 to supply oxygen in vessel 11. The amount of additional air introduced from line 15 should be controlled so that the oxygen content of gases in condenser 20 and receiver 21 will be less than 8 percent, preferably near zero. Condensate from receiver 46 is returned by line 47 to line 12 for introduction into vessel 11 although, if desired, a part of this condensate may be returned to vessel 33 and/ or introduced by line 24 to still 25. By introducing substantially anhydrous acetic acid into oxidizer 33, the solvent in this vessel remains substantially anhydrous since the water formed by oxidation is largely removed with solvent vapors through line 44 and the solvent thus removed supplies most of the required solvent for vessel 11 as hereinabove described.
The product stream is withdrawn from the base of vessel 33 by line 48 and introduced by pump, reducing valve, or other transfer means 49 to crystallizer 50 which may be operated at any pressure in the range of atmospheric to 100 p.s.i. or more and in this example is operated at about l p.s.i.g. Solvent vapors are removed from the crystallizer by line 51 through condenser 52 and the condensate and vapors are thence introduced into receiver 53 from which condensate passes by line 54 to line 24 and still 25 While vapors pass by line 55 to line 26 and scrubber 27. A portion of the condensate may be recycled to crystallizer 50 to maintain a pumpable slurry. Slurry is removed from the base of the crystallizer by pump 56 and introduced by line 57 to separator 5S which may be a suitable iilter or centrifuge system. Crystals separated in separator 53 may be Washed with a wash liquid from line 59 (water or acetic acid), the wash liquid being returned by pump 60 and line 61 back to crystallizer 50. If wash is acetic acid, this may be sent to either oxidizer 11 or 33 for makeup if desired. During the wash cycle, slurry discharged by pump 56 may be returned to vessel 50 by line 62. Washed crystals of terephthalic acid are discharged from the system by line 63.
The mother liquor which is discharged from separator 58 by line 64 is separated in system 65, preferably by fractionation, into various components such as aqueous solvent which is discharged by line 66 to line 24 and still 25, a toluic acid fraction which is recycled by line 40 to oxidizer 33, a product fraction withdrawn through line 67 (which may be benzoic acid if the charge contains ethylbenzene) and a waste fraction withdrawn 4through line 68.
The aqueous solvent from all parts of the system is charged by line 24 to still 25 from which substantially anhydrous solvent is withdrawn through line 69 to storage tank 70 from which such solvent is returned by pump 71 and line 72 to supply the requirements of vessel 33. Water and azeotroped unreacted hydrocarbons are taken overhead through line 73 and condenser 7d to receiver 75 from which hydrocarbons may be withdrawn by line 76 and water through line 77, a part of the condensed water being returned by pump '7S and line 79 for use as reliux in still 25.
While the invention has been described as a system for producing terephthalic acid from paraxylene, it should be understood that the invention is applicable to the oxidation of any aromatic hydrocarbon having one or more, and preferably at least two, oxidizable substituents. Examples of oxidizable substituted aromatic hydrocarbons and of the acids obtained therefrom are as follows:
Methylbenzene Benzoic. 1,2-dmiethy1benzene- Phthalic. 1,3-dimethy1benzene sophthalic. 1,--dimethylbenzene Terephthalc. 1,2,3-trimethylbenzene Heminielhtic.
Trimesic. Prehnitic. Pyroinelliltic. Mellophanic.
1,3 5-t1imethylbenzene l,2,3,4-tetramethylbenzene- 12,4,5-tetramethylbenzene 1,2 3,5-tetramethylbenzenel-methylnaphthalene a-Naphthoic acid. 2-methylnaphthalene -Naphthoic acid.
In al1 cases the oxidation is preferably effected in the presence of known oxidation catalysts and also in the presence of a bromine-atording substance; this type of oxidation not only results in minimizing degradation and by-product formation but it enables the use of air or other oxidizing gas as the oxidizing medium and hence minimizes the presence in the final products of certain of the impurities which are usually present in oxidation processes produced by other techniques. The temperatures, pressures, contact times and so forth will, ofcourse, be dependent upon the particular charging stock employed and the nature and purity of the desired acid product. A specific example of my invention has been described in considerable detail and various alternative arrangements, steps and conditions will be apparent from said description to those skilled in the art.
l. The method of oxidizing a polyalkyl aromatic hydrocarbon in the liquid phase to an aromatic polycarboxylic acid, which method comprises introducing such hydrocarbon into a first oxidizing zone and therein contacting it with gas containing molecular oxygen and an oxidation catalyst at a temperature in the range of about 300 to 400 F. under a pressure of the order of 50 to 400 p.s.i., pumping liquid from the irst oxidation zone to a second oxidation zone and also pumping to the second oxidation zone at least an equal volume of substantially anhydrous aliphatic carboxylic acid containing 2 to 6 carbon atoms as solvent, electing oxidation in the second zone in the presence of an oxidation catalyst comprising bromine promoted multi-valent heavy metal in an amount of from 0.01 to l0 percent based on said aromatic hydrocarbon wherein the ratio of bromine promoter is in the ratio of 0.1 to l0 atoms of said heavy metal per atom of bromine at a temperature in the range of 320 to 440 F. at higher pressure in the range or to 500 p.s.i. by introducing a controlled amount of ox Igen-containing gas at the base of the second zone, removing soivent in the form of vapors from the second oxidation zone and S3 returning said removed solvent to said first oxidation zone in an amount at least equal to that or poiyalkyl aromatic hydrocarbon introduced thereto, condensing soivent vapors leaving the first oxidation zone and returning to said iirst zone at least a part of condensed vapors.
2. The method of claim 1 which includes the step of ashing liquid from the rst oxidation zone before it is pumped to the second oxidation zone to separate unoxidized hydrocarbons in Vapor form and returning said separated hydrocarbons to the rst oxidation Zone.
3. The method of countercurrently oxidizing a polyalkyl aromatic in the liquid phase to an aromatic polycarboxylic acid charging stock in a plurality of stages in the presence of a solvent and catalyst comprising bromine promoted multi-valent heavy metal in an amount of from 0.01 to 10 percent based on said aromatic hydrocarbon wherein the ratio of bromine promoter is in the ratio of 0.1 to 10 atoms of said heavy metal per atom of bromine, which method comprises adding substantially anhydrous acetic acid and air to the iinal stage, adding both oxidizing gas and recovered solvent from the final stage to an earlier stage, passing a charging stock to be oxidized to the earlier stage and passing partially oxidized charging stock from the earlier stage to the nal stage.
4. The method of oxidizing p-xylene in the liquid phase with air to terephthalic acid in the presence of acetic acid which method comprises introducing into the rst of two oxidation zones a mixture consisting essentially of acetic acid, para-Xylene and an oxidation catalyst comprising bromine promoted multivalent heavy metal in an amount of from 0.01 to 10% based on para-xylene wherein the ratio of bromine to heavy metal is in the ratio of 0.1 to l0 atoms ot said heavy metal per atom of bromine wherein said mixture there is on a volume basis a ratio of acetic acid to para-xylene of from 1:1 to 5:1, contacting para-xylene in said rst oxidation zone with air at a pressure in the range of from 50 to 400 p.s.i. and at a temperature in the range of from 300 to 400 F., flashing liquids from the iirst oxidation zone to separate unoxidized para-xylene in vapor form, returning said unoxidized paraxylene -to the first oxidation zone, pumping liquid from said flashing step to the second oxidation zone and also pumping to the second oxidation zone at least an equal volume of anhydrous acetic acid, contacting the mixture in the second oxidation zone with air at a pressure in the range of 100 to 500 p.s.i. and at a temperature in the range of 320 to 440 F., removing acetic acid vapors from the second oxidation zone and adding at least a portion of said acetic acid vapors in the rst oxidation zone, condensing acetic acid vapors leaving the rst oxidation zone and returning to the first oxidation zone at least a part of the condensed acetic acid.
References Cited in the tile of this patent UNITED STATES PATENTS 2,245,528 Loder June 10, 1941 2,552,267 Emerson et a1. May 8, 1951 2,746,990 Fortuin et al. May 22, 1956 2,833,816 Saifer et al May 6, 1958 FOREIGN PATENTS 666,709 Great Britain Feb. 20, 1952 UNITED STATES- PATENT oFFIcE CERTIFICATE 0F CORRECTION Patent Noo 3,064,044 November 13, 1962 I Richard H. Baldwin v It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, line 40, for "or" read of column 3, line 17, for "terphthalic", read terephthalic column 4, in the table, line 2 thereof, for "dimiethylbenzene" read dimethylbenzene same table, second column, line 9 thereof,
for "Pyromelliltic" read Pyromellitic column 5, line 12, after "aromatic", first occurrence, insert charging stock line 13, after "acid" strike out vcharging stock c Signed and sealed this 7th day of May 1963.
`ERNIEIST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents